Silicate and titanate orthoesters and soil-proofed textile materials



United States Patent C) l 3,342,630 SILICATE AND TITANATE ORTHOESTERS AND SiHL-PROOFED TEXTILE MATERIALS Domeniclc Donald Gagliardi, East Greenwich, R.I., as-

signor to Colgate-Palmolive Company, New York,

N.Y., a corporation of Delaware No Drawing. Filed Sept. 13, 1963, Ser. No. 308,639

7 Claims. (Cl. 117-1395) The present invention relates to the preparation of silicate and titanate orthoesters of fluorinated alcohols and to soil-proofed textiles produced by treatment of textiles therewith.

Since the early years of the nineteenth century man has sought to impart water-repellency and more recently oil-repellency to textiles. However, few, if any, of these prior arts attempting to produce waterand oil-repellent textiles were soil-repellent. That is to say, the textiles sotreated while water-repellent and/or oil-repellent when contacted with oily, particulate-soil attracted rather than repelled such oily particulate-soil.

Oily, particulate-soil is best illustrated by the grime, i.e., finely divided dirt and oily exudations of the human skin, which accumulates from the environment on the collars and cuffs of mens shirts and face powder, makeup and the oily exudations of the human skin which accumulates on the neckbands of womens blouses.

Those skilled in the art will recognize that for the evaluation of the comparative effectiveness of treating agents to repel such oily, particulate-soil any test based upon comparison of finishes applied and used in daily life is doomed to failure because of the inability of the investigator to control (1) the manner in which the oily, particul-ate-soil is accumulated, (2) the amount of oily, particulate-soil accumulated, and (3) the composition of the oily, particulate-soil and, hence, the tenacity with which the oily, particulate-soil is held by the treated textile. Accordingly, it has been necessary to employ an investigating procedure in which the composition of the oily, particulate-soil is known and controlled, in which the amount of oily, particulate-soil accumulated on the test pieces is uniform, and the manner in which the oily, particulate-soil is accumulated is uniform. The following investigative procedure provides such uniformit Composition of oily, parZiculate-soil (American Cyanamid Synthetic Soil) The following dry ingredients are blended thoroughly, dried in a forced draft convection oven for eight hours at 50 C., then milled for twenty-five hours with ceramic balls and stored in a polyethylene bag:

1 R. T. Vanderbilt Peerless. 2 Davison Chemical Co.

3 Bandy and Smith Molacco. 4 C. K. Williams Co.

Depositin.-Fifteen to twenty 6" x 8" numbered specimens (usually 80 x 80 cotton), including at least one untreated control, are tumbled for thirty minutes with ten percent of the aforedescribed oily, particulatesoil based on the Weight of the fabric. The tumbling is carried out in a five liter capacity Five Minute Home Cleaner 3,342,630 Patented Sept. 19, 1967 ICC at 44 rpm. Six No. 8 Neoprene rubber stoppers are distributed among the specimens to increase mechanical action. At the end of the tumbling, the specimens are removed and each individually shaken up and down fifteen times to remove surface dirt.

Evaluati0n.-The so-soiled specimens are then cut into two pieces (to produce two 4" x 6" pieces). One half is washed with fifty grams of FAB in a cotton cycle with a five pound dummy load, hung to dry, and lightly ironed under a clean cotton cloth.

The degree of soiling is determined with a Photovolt Reflectance Meter using a Tri Blue Filter. Six readings are taken on each unwashed specimen and reported as reflectance before washing. This is an evaluation of the effectiveness of the finish provided by the treating agent to repel oily, particulate-soil. Six readings are taken on each washed specimen. This is an evaluation of the effectiveness of the finish provided by the treating agent to release any accumulated oily, particulate-soil during laundering. The arithmetic average of each of the six readings is reported. The higher the reflectance the more efficient is the finishing agent in repelling and/or releasing the oily, particulate-soil.

While for many finishing applications it is manifest that the effectiveness of a finishing agent to repel rather than attract and to shed rather than retain oily, particulatesoil is of primary importance, the effectiveness of a finishing agent to impart waterand/or ioil-repellency to a treated textile is of interest also. For the determination of the water-repellency imparted to a textile there is the AATCC Standard Test Method 22-1952 generally known as the Spray Test. For the determination of the oilrepellency conferred upon a textile there is the 3M Oil Repellency Test described in the publication of the Minnesota Mining and Manufacturing Company entitled 3M Textile Chemicals at Appendix A-Test Methods, Page 1.

Spray Test (Resistance to Wetting).-This test method is applicable to any textile fabric. It measures the resistance of fabrics to wetting by a water spray and the results depend primarily on the degree of hy-drophobicity inherent in the fibers and yarns and subsequent treatments applied to the fibers and yarns. Water is sprayed against the taut surface of a test specimen. Evaluation of the wetted pattern is readily brought about by comparing the wetted pattern with standard wetting pattern pictures. The ratings are numerical and have the following significances.

100No sticking or Wetting of the upper surface. 90Slight random sticking or wetting of the upper surface. -Wetting of the upper surface at the spray points. 70Partial wetting of the whole of the upper surface. 50-Complete wetting of the whole of the upper surface. OCom-plete wetting of the whole of the upper and the lower surfaces.

When measuring the spray rating, it is not unusual to encounter a test specimen with sufiicient hydrophobic properties to confine the area of wetting and yet permit wetting through. The following illustrates the report of such a condition.

Thus a spray rating number 70/0 indicates a spray rating of 70 while the 0 in the denominator indicates wetting to the under surface of the cloth at the wet areas.

The test specimens of a minimum size of 7" x 7 are conditioned at 70 F. and 65 percent relative humidity for a minimum of four hours before testing. 7

The test specimen, fastened securely and wrinkle-free in a metal hoop having a diameter of six inches, is placed and centered six inches under a standard spray nozzle at an angle of 45 degrees to the horizontal. Two hundred and fifty milliliters of water at 80i2 F. is poured into the funnel attached above the spray nozzle. The spray lasts 25-30 seconds at the end of which time the hoop is taken by one edge and the opposite edge tapped smartly once against a solid object with the Wet side facing the solid; this procedure is repeated with the hoop reversed 180 degrees.

Oil repellency te'st.The Minnesota Mining and Manufacturing Company oil repellency test is based on the dilference of penetrating properties of two hydrocarbon liquids, heavy mineral oil (Nujol) and n-heptane. The Nujol-heptane proportions for each rating were selected by 3M to give oily stain resistance somewhat comparable to the water-borne stain resistance corresponding to each of the spray ratings of the AATCC Standard Test Method 22-1952 described hereinbefore.

The standard oil-heptane mixtures are contained in small stoppered medicine dropper bottles. A drop of each mixture is placed on the fabric. The appearance of the test oil is observed through the drop. The occurrence of wetting or penetration is noted. The number corresponding to that mixture containing the highest percentage of heptane which does not penetrate or wet the fabric after three minutes is considered the oil repellency rating of the finish.

The change in the optical refractivity of the drop is often an indication of wetting. In some cases wetting can be better determined by observing the other side of the fabric. In some cases of oil/heptane rating, the term 0+ has been used to indicate a modicum of resistance to wetting by oil.

The numerical values of the Oil Repellency Rating and the significance thereof are tabulated in the following:

1 No holdout to Nujol.

Since resistance to soiling by water-borne and/ or oilborne stains is also of importance in the finishing of household furnishing such as rugs, sheets, curtains, draperies, wearing apparel and the like, a test for evaluating the capacity of treating agents such as the novel orthoesters of the present invention to confer resistance to staining by coffee, salad oil, tea, ketchup, grape juice, ink and similar waterand/or oil-borne stains encountered in the every day environment is desirable and has been developed.

Waterand/0r oil-repellency test.The fabrics are streatched lightly on 12 x 31" frames. All or part of the frame area is used depending on the amount of fabric available. The frames are supported at both ends with the fabric about eight inches above a black horizontal surface. The fabric is in contact with nothing but the frame.

Three inch medicine droppers are used to draw the stains from their containers. A one cubic centimeter calibration is established, and marked on the exterior of each dropper. The stains are squeezed vertically downward from a height of two inches above the fabric.

After five minutes the unabsorbed stain is wiped off the fabric with two sweeps of Kleenex and the stain rated.

Duplicate sets of stains are applied in separate areas so that one half of the fabric can be washed. The wash is carried out with fifty grams of FAB, a cotton cycle, and a dummy load to total five pounds in a Norge Home Automatic Washer.

The stains employed are as follows:

Water stains Instant Tea, Tetley a Salad Mustard (Ann Page) Sheaffers 232 Blue-Black Chocolate Syrup (Bosco) l rip Concord Grape Juice Oil stains Oleomargarine b Tomato Sauce Wesson Oil Gulf Supreme Motor Oil 20/20 Hand Lotion (Jergens) 8 cubic centimeters dry powder per 200 cubic centimeters of water (applied at F.).

b Melted and applied at 160 F.

Stain ratings The finishing agents or soil-repellent agents of the present invention are silicate and titanate orthoesters of fluorinated aliphatic alcohols in which at least 70 percent of the hydrogens, other than the hydroxyl hydrogen, has been replaced with fluorine and in which the terminal carbon atom is attached to at least two, and preferably three, fluorine atoms. In general, the orthoesters of the present invention have compositions corresponding to the formula where X is Si or Ti; R is an alkyl group having one to six carbon atoms; Q is the fluorinated alkyl group of any aliphatic alcohol having one to twenty-two carbon atoms and three to forty-five hydrogen atoms of which at least seventy percent has been replaced by fluorine and the terminal group is CHF and preferably CF n is zero to three; and m is four to one.

These orthosilicates and orthotitanates are produced in any suitable manner. Presently, it is preferred to prepare the orthoesters by ester interchange. Thus, the orthosilicates of C -perfiu0roalc0h0l were prepared as follows: One equivalent of ethylorthosilicate was reacted with four equivalents of C perfluoroalcohol lH,ll-I,11H eicosafluoro-l-undecanol [CHF (CF CH OH] in the presence of a catalytic small amount of sodium methoxide (1 gram). About one-third of the theoretical amount of ethanol to be produced in a complete ester interchange was collected leaving a residue which was predominantly a mixture of orthosilicates having up to four fluoroalkyl radicals per molecule.

In a similar manner the orthotitanate of the C -perfluoroalcohol was prepared. That is to say, four equivalents of the C -perfluoroalcohol were dissolved in about 710 milliliters of xylene. The Xylene solution was heated and one equivalent of tetrabutyltitanate was added. The xylene-and liberated butyl alcohol were removed by vacuum distillation. A brownish solid soluble in cold methanol remained as a residue of the vacuum distillation.

A mixture of C -perfluoroalkyl orthotitanates was prepared as follows: Four equivalents of C -perfluoroalcohol and one equivalent of tetrabutyltitanate were dissolved in ethyl ether. The solution was agitated for about thirty minutes and allowed to stand for about sixty hours. The ethylether was removed at atmospheric pressure. Five grams of distillate were removed at reduced pressure leaving a yellow residue which solidified to a tan-colored, waxy solid, soluble in isopropanol.

The silicate and titanate orthoesters of the fluorinated alcohols are applied to the textile material or substrate either from solution in suitable solvents such as C to C aliphatic alcohols, acetone, toluene, hexane, and heptane or from emulsions using a surfactant such as triethanolaminelaurylsulfonate, sorbitol monostearate and other non-rewetting surfactants. The orthoester or esters of a fluorinated alcohol or a mixture of orthoesters of fluorinated alcohols is applied to the substrate in any suitable manner. For example, the fabric for illustrative purposes 80 x 80 cotton is padded one dip, one nip through the solution or dispersion of the orthoester or esters preferably containing an alkaline catalyst such as sodium bicarbonate, potassium hydroxide and triethanolamine or an acid catalyst such as phosphoric acid, oxalic acid, and zinc chloride. After impregnation with the solution or dis persion of the orthoester or esters the treated substrate is dried and heat treated at a temperature in the range of room temperature (circa 70 F.) and 350 F. for a period inversely as the temperature and for example about twenty-four hours at 70 F.

Cotton padded as described hereinbefore with the reaction product of tetrabutyl orthoester of titanium and C trihydrofluoroalkyl alcohol 1H,1H,11H-eicosafluoro- 1-undecanol [CHF (CF CHOH] in a 1:4 mol ratio had the repellencies indicated by the numerical values tabulated hereinafter.

Percent solids in bath 3 Cured at room temperature Repellency:

Spray 50/0 Oil 70 Reflectance:

B 37 A 68 Cured at 300 F. for 5 mins.-

Repellency:

Spray 5 O/ Oil 0 Reflectance:

It will be observed that the foregoing results are exemplary of results obtained without the use of either an alkaline catalyst or an acid catalyst. When a catalyst is to be used, the catalyst is incorporated in the padding bath in concentrations of about 0.5 to about 1.0 percent by weight based upon the weight of the treating solution.

The novel silicate and titanate orthoesters of fluorinated alcohols (corresponding in composition to the generic formula (RO) (OQ) given hereinbefore) of the present invention are not to be confused with products previously described. For example, in US. Patent No. 2,709,174 there are described products conforming to the formula TiY (ORY) where Y is a halogen such as chlorine or bromine, R is an alkylene or rolefinyl group either substituted or unsubstituted and x has the value of 0 to 3. As the patentees state these products may be dissolved in solvents and subjected to partial hydrolysis, or they may be directly subjected to hydrolysis and the partial hydrolytic and condensation products used as protective coatings, adhesives, binders, textile-treating agents and the like, or they maybe mixed with other organo titanium derivatives and employed in any of the manners set forth.

In US. Patent No. 2,892,859, the use of products corresponding to the formula (XR O),,Si(R) wherein n represents an integer 2 or 3, X represents a lower perfluoroalkyl group having one to eight carbon atoms, R 0 represents lower alkenoxy group having one to five car bon atoms, and R represents alkyl as snufler agents and lubricant additives. It will be observed that while the novel orthoesters of the present invention are waxy solids the products described in US. No. 2,892,859 are liquids 6 at room temperature, having boiling points from about centigrade to about 200 centigrade.

The disclosure of US. Patent No. 2,928,857 relates to organic compounds of silicon containing polyfluoroalkoxy groups derived from tetrafluoroethylene/ alcohol telomers. The polyfluoroalkoxy silanes described in U.S. Patent No. 2,928,857 have the following general formula:

wherein R is a monovalent hydrocarbon radical free from aliphatic unsaturation, n is 4, 6, or 8, x and y are positive integers from 13, inclusive, i.e., integers having a value of 1, 2, or 3, and the sum of x-l-y equals 4. The polyfluoroalkoxysilanes described in US. Fatent No. 2,928,857 in view of their high thermal stability and good lubricating qualities are of great value as lubricants especially for use at high temperatures. Those polyfluoroalkoxysilanes boiling above 200 C. described in US. 2,928,857, are useful components in liquid polishes for glass and painted surfaces and in easy rubbing, self-polishing waxes.

The fluorinated carbinoxysilanes and polymers thereof are useful in the surface treatment of metals. Thus, the patentee states that he has found that a preliminary application of his (1,1-dihydroperfluorobutoxy) dichlorosilane to the aluminum surface provides ahighly effective bonding action between the metal and a subsequently applied coating of plastic fluorinated sealer material for aircraft sealers designed to leakproof the wing section fuel tanks of all-metal aircraft. The carbinoxysilane compounds described in US. Patent No. 2,993,925 have the generic formula:

where Rf is a fluorinated alkyl radical containing only carbon and fluorine atoms, X is a member of the class consisting of halogen atoms and amino groups, and x is 1-4.

The silanes described in US. Patent No. 3,038,000 have the formula:

where R is a monovalent hydrocarbon radical, X is a member selected from the class consisting of hydrogen and fluorine, m is an integer equal to at least 2, e.g., from 2 to 16 or more, n is an integer equal to at least 2, e.g., from 2 to 6 or more, a is 0 or 1, b is 2 or 3, and the sum of a+b is equal to 3.

The carboperfluorooxyalkylsiloxane fluids prepared in Examples 2 through 5 of the US. Patent No. 3,038,000 have structures conforming to the formulae:

HF C (CF CH OOC (CH SiO (EX. 2) HF C CF CH OOC (CH SiO (EX. 3) F C(CF CH OOC(CH SiO (EX. 5)

These prior art siloxanes were dissolved in xylene mixed with a curing catalyst, padded onto cotton cloth and cured six minutes at C. The treated cloth was then subjected to spray rating tests similar to those described in the 1945 yearbook of the American Association of Textile Chemists and Colorists, Vol. XX, pages 229-233. It is to be observed that in these tests the cotton was padded from a solution made by adding two parts of silicone fluid to 100 parts by weight of xylene and 0.1 part of a 28 percent tin octoate solution in xylene was added to the mixture. The spray ratings of each material of the examples is given in the patent as follows- Spray Rating It will be observed that the oil repellency of the patented silicone fluid was not determined. It will also be observed that the particulate soil repellency was not determined. It will further be observed that the silicones of US. Patent No. 3,038,000 are fluids whereas the orthoesters f the present invention are waxy solids. Finally, it will be observed that the patented silicone fluid was padded on the cloth in the presence of the catalyst tin octoate whereas the mixture of orthotitanates of perfluoro-C alcohol were padded on the cotton in the absence of added or known catalyst.

In US. Patent No. 3,070,617 cyclic siloxanes useful in the preparation of copolymers of bistrifluoropropylsiloxane with other siloxanes such as trifluoropropylmethylsiloxane, diphenylsiloxane and the like are described. The patented cyclic siloxanes conform to the formula where n is an integer from 3 to 4 inclusive. It will be observed that in the patented cyclic siloxanes only the terminal carbon of the alkyl moiety is attached to fluorine atoms. In other words, CH CH CH only three of seven hydrogen atoms or only forty-three percent of the hydrogens of the alkyl group has been replaced by fluorine atoms where as in the orthoesters of the present invention at least 70 percent of the hydrogen atoms of the alkyl group of the aliphatic alcohol has been replaced by fluorine atoms.

Although the presently preferred method of preparing silicate and titanate orthoesters of fluorinated alcohols is through the classical method of ester interchange, applicant does not claim as his invention the ester interchange catalyst per se. In contrast in US. Patent No. 2,820,806 the ester interchange catalyst Ti(OR) where R is a hydrocarbon radical and preferably is isopropyl or butyl is described.

Those skilled in the art will recognize that, with the exception of the description of the use of the fluorinecontaining materials conforming to the generic formula (US. Patent No. 3,038,000) for imparting water repellency to cotton cloth, none of the fluorine-containing materials described in the US. patents discussed hereinbefore are concerned with imparting water and/ or oil repellency to textile materials. Furthermore, there is no suggestion in any of the patents discussed hereinbefore that any of the fluorine-containing materials described in these US. patents impart to or confer on textile materials treated therewith with the capability to repel oily, particulate soil as do the silicate and titanate orthoesters of fluorinated alcohols of the present invention.

What is claimed is: 1. Waxy solids having a composition corresponding to the formula )n Q)m where R is an alkyl group having one to six carbon atoms, Q is the fluorinated alkyl group of an aliphatic alcohol having one to twenty-two carbon atoms and three to fortyfive hydrogen atoms of which at least percent has been replaced by fluorine and the terminal group is selected from CHF and CF n is 0 to 3; m is 4 to 1; and x is selected from the group consisting of Si and Ti.

2. A compound as defined in claim 1 wherein the aliphatic alcohol is 1H,1H,11H-eicosa-fluoro 1 undecanol and X is Ti.

3. Textile material having affixed thereto in soil repellent amount a waxy solid as defined in claim 1, where R is an alkyl group having one to six carbon atoms, Q is the fluorinated alkyl group of an aliphatic alcohol having one to twenty-two carbon atoms and three to fortyfive hydrogen atoms of which at least 70 percent has been replaced by fluorine and the terminal group is selected from CHF and CF n is 0 to 3; m is 4 to 1; and X is Si or Ti.

4. Textile material as defined in claim 3 wherein the aliphatic alcohol is 1H,1H,11H eicosa-fluoro-l-undecanol and X is Ti.

5. Textile material having affixed thereto in soil repellent amount, a waxy solid as defined in claim 1, said textile material and waxy solid having been cured at a temperature in the range of room temperature to 350 F. for a period inversely as the temperature and about twenty-four hours at room temperature.

6. Textile material as set forth in claim 5 wherein curing is carried out in the presence of acid catalyst.

7. Textile material as set forth in claim 5 wherein curing is carried out in the presence of alkaline catalyst.

References Cited UNITED STATES PATENTS 2,878,144 3/1959 Conbere et al 117139.5 2,878,273 3/1959 Conbere et a1. 117-l39.5 X 2,892,859 6/1959 McBee et al. 260-448.8 2,917,409 12/1959 Green 117121 WILLIAM D. MARTIN, Primary Examiner.

T. G. DAVIS, Assistant Examiner. 

1. WAXY SOLIDS HAVING A COMPOSITION CORRESPONDING TO THE FORMULA
 3. TEXTILE MATERIAL HAVING AFFIXED THERETO IN SOIL REPELLENT AMOUNT A WAXY SOLID AS DEFINED IN CLAIM 1, WHERE R IS AN ALKYL GROUP HAVING ONE TO SIX CARBON ATOMS, Q IS THE FLUORINATED ALKYL GROUP OF AN ALIPHATIC ALCOHOL HAVING ONE TO TWENTY-TWO CARBON ATOMS AND THREE TO FORTYFIVE HYDROGEN ATOMS OF WHICH AT LEAST 70 PERCENT HAS BEEN REPLACED BY FLUORINE AND THE TERMINAL GROUP IS SELECTED FROM CHF2 AND CF3; N IS 0 TO 3; M IS 4 TO 1; AND X IS SI OR TI. 